Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers

ABSTRACT

Copolymers of a carboxylic acid monomer and one or more higher, that is 10 to 30 carbon atoms, alkyl acrylate esters surprisingly serve as efficient thickeners of aqueous solutions, even in the presence of substantial amounts of inorganic salts such as sodium chloride.

United States Patent [1 1 Schlatzer, Jr.

[ UNSATURATED CARBOXYLIC ACID-LONG CHAIN ALKYL ESTER COPOLYMERS AND TRI-POLYMERS WATER THICKENING AGENTS AND EMULSIFIERS [75] Inventor: Robert K. Schlatzer, Jr., Bainbridge Township, Ohio [73] Assignee: The B. F. Goodrich Company, Akron, Ohio [22] Filed: July 2, 1974 [21] Appl. No.: 485,125

[52] US. Cl. 260/l7.4 SG; 260/78.5 R; 260/78.5 T; 260/86.1 R; 260/89.5 R

[51] Int. Cl. C08F 218/02; COSL 5/00; C08F 218/14 [58] Field of Search 260/l7.4 SG, 80.3, 861 R, 260/80, 81, 78.5 R, 78.5 T, 89.5 R

[56] References Cited UNITED STATES PATENTS 2,533,376 12/1950 Jones ..260/78.5

[4 1 Oct. 28, 1975 OTHER PUBLICATIONS Chem. Abst., 67:12156b, Aqueous Colloidal Dispersion of Acrylic Polymers, du Pont.

Primary Examiner-Donald E. Czaja Assistant Examiner Edward Woodberry [57] ABSTRACT Copolymers of a carboxylic acid monomer and one or more higher, that is 10 to 30 carbon atoms, alkyl acrylate esters surprisingly serve as efficient thickeners of aqueous solutions, even in the presence of substantial amounts of inorganic salts such as sodium chloride.

7 Claims, No Drawings UNSATURATED CARBOXYLIC ACID-LONG CHAIN ALKYL ESTERCOPOLYMERS AND TRI-POLYMERS WATER THICKENING AGENTS AND EMULSIFIERS BACKGROUND OF THE INVENTION It is known (US. Pat. No. 2,798,053) that copolymers of carboxylic monomer such as acrylic acid and about 0.1 to LG by weight of a polyalkenyl polyether crosslinker such as polyallyl sucrose are gel-like polymers which are insoluble in water and organic solvents and which, especially in the form of their salts, absorb large quantities of water or solvent with consequent many times increase in volume. Additional monomers taught by the patent as compatible with 40% to 95% by weight acrylic acid and 0.2% to 2.5% by weight polyalkenyl polyether are 4% to 59% by weight methyl acrylate and Z-ethylhexyl acrylate. These polyelectrolyte polymers are useful as bodying and suspending agents in various mucilaginous and colloidal gel-like applications such as dentifrices, surgical jellies, creams and ointments, printing paste thickeners, and the like. A still unsolved problem is that most polyelectrolyte solutions decrease drastically in viscosity uponthe addition of electrolytes such as sodium chloride. The prior art thickener materials are ion-sensitive and do not serve to efficiently maintain or increase the viscosities of water or organic solvent solutions containing inorganic salts such as sodium chloride even when a third monomer such as 2-ethylhexylacrylate is included in the polymer as is suggested by the prior art patent. This property would be of great value, for instance, in thickening certain latexes, oil well drilling muds, food preparations, ionic detergents, dye pastes, cosmetic preparations, and pharmaceuticals. In some cases the problem is to thicken a solution containing a given amount of salt, as in a particular pharmaceutical recipe. In other cases it may be desired to maintain a constant viscosity level in a solution in which the amount of salt present is increasing for example, in an automobile storage battery.

SUMMARY OF THE INVENTION Polymers of a carboxylic acid monomer and one or more acrylic esters having aliphatic chain length of to carbon atoms are found to be efficient water thickeners which, when neutralized by a basic material, form water mucilages that have much greater resistance to dropping sharply in viscosity when a salt such as sodium chloride is either added thereto, or is already present in said water system, than do the mucilages prepared with thickening agents known in the prior art.

Depending on the proportion of the critical long chain aliphatic acrylates utilized, the polymers vary considerably in properties. Varying the proportion of the acrylate monomer serves to provide control of aqueous solution viscosity of the copolymer solutions, control of the rheology or flow properties of combinations of polymer and a solvent such as water, and to provide the ability to thicken ion containing water solutions with an efficiency heretofore not possible with prior art thickening agents.

The new copolymers provided by this invention may optionally be crosslinked by the inclusion in the polymer system of a crosslinking monomer selected from polymerizable compounds containing a polymerizable CH2 =C grouping and at least one other polymerizable grouping, the unsaturated bonds of said polymerizable grouping being nonconjugated with respect to each other.

When an optional crosslinking monomer is present, it serves to provide particular control of the rheology of the mucilage. With no crosslinker present, thickening agents containing less than 20-30 weight percent of acrylate ester often form solutions which are stringy in nature before a salt is added, but which become desirably smooth and buttery in appearance after the addition of salt. A solution or mucilage of a crosslinked thickener of this invention containing a suitable level of long chain alkyl acrylate or methacrylate is usually buttery in its initial appearance and maintains more constant solution viscosity in cases where salt is added to the solution in increasing amounts than do the prior art materials.

DETAILED DESCRIPTION OF THE INVENTION Highly useful carboxylic polymers are obtained when a carboxylic monomer such as acrylic acid, maleic acid or maleic anhydride, and the like is copolymerized with certain proportions of acrylic esters having long chain (from 10 to 30 carbon atoms) aliphatic groups and, optionally, with a crosslinkingagent comprising a polymerizable compound containing a polymerizable CH2 =C grouping and at least one other polymerizable grouping, said groups being nonconjugated with respect to each other. These crosslinkers are typified by allyl acrylate, methallyl methacrylate, diallyl malonate, divinyl ether, glycol diacrylate (ethylene diacrylate), glyceryl triacrylate, and divinyl benzene.

A useful crosslinking material is a polyalkenyl polyether of a polyhydric alcohol containing more than one alkenyl ether grouping per molecule, the parent polyhydric alcohol containing at least four carbon atoms and at least three hydroxyl groups, typified by polyallyl sucrose.

In aqueous systems where a relatively constant vicsosity is to be maintained as the amount of an inorganic salt added to the system is increased from about 0.05 to about 3.0 percent by weight, the presence of a crosslinking monomer is generally beneficial. The presence of the crosslinking material in these solutions maintains the texture of the solution. This is particularly important in pharmaceutical and cosmetic applications. Some thickened aqueous solutions are stringy in nature, appearance and feel. This texture may change to a more desirable buttery or smooth consistency as salt is added. The smooth texture can be usually achieved initially and can be easily maintained upon the addition of salt if a crosslinking monomer is present.

Crosslinking monomers in the thickening compositions of this invention are not needed nor preferred if the neutralized copolymer is to be used to thicken an aqueous system which initially contains salt ions (the salt being present at a level of 0.5 to 5 percent by weight in the solution). The brines encountered in oil well drilling are instances of this situation.

Many of the compositions of this invention are superior to gum tragacanth, gum Karaya and other naturally occurring more or less insoluble gum-like substances conventionally used as bodying and suspending agents. The high swelling polymers of this invention are useful in preparing various mucilaginous or colloidal gel-like materials such as dentifrices, surgical jellies, creams and ointments, and printing paste thickeners. They show promise as foam builders and foam stabilizers and as emulsifying agents for water-solvent combination compositions. They also find use in low concentrations by weight as treatment agents for waste water, cooling water and boiler water. In liquid detergent solutions the copolymers serve as clarifying or solubilizing agents as well as thickeners.

Production of the polymers of this invention employs a monomeric mixture which contains two essential monomeric ingredients, each in certain proportions, one being a monomeric olefinically unsaturated carboxylic acid and the other being an acrylic ester having a long chain aliphatic group. Optionally, there is included in the monomeric mixture a crosslinking monomer, for example, allyl sucrose.

The carboxylic monomers useful in the production of the polymers of this invention are the olefinically unsaturated carboxylic acids containing at least one activated carbon-to-carbon olefinic double bond, and at least one carboxyl group, that is, an acid containing an olefinic double bond which readily functions in polymerization because of its presence in the monomer molecule either in the alphabeta position with respect to a carboxyl group thusly,

or as a part of a terminal methylene grouping thusly, CH =C In the alpha-beta acids the close proximity of the strongly polar carboxyl group to the doublebonded carbon atoms has a strong activating influence rendering the substances containing this structure very readily polymerizable. The presence of a terminal methylene grouping in a carboxylic monomer makes this type of compound much more easily polymerizable than if the double bond were intermediate in the carbon structure. Olefinically-unsaturated acids of this class include such widely divergent materials as the acrylic acids typified by acrylic acid itself, methacrylic acid, ethacrylic acid, alpha-chloro-acrylic acid, alphacyano acrylic acid, beta methyl-acrylic'acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, alpha-chloro sorbic acid, angelic acid, cinnamic acid, p-chloro cinnamic acid, beta-styryl acrylic acid (l-carobxy-4-phenyl butadiene-l,3), ita conic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, and tricarboxy ethylene. As used herein, the term carboxylic acid includes the polycarboxylic acids and those acid .anhydrides, such as maleic anhydride, wherein the anhydride group is formed by the elimination of one molecule of water from two carboxyl groups located on the same polycarboxylic acid molecule. Anhydrides of the types formed by elimination of water from two or more molecules of the same or different unsaturated acids, such as acrylic anhydride, are not included because of the strong tendency of their polymers to hydrolyze in water and alkali. Maleic anhydride and the other acid anhydrides useful herein have the general structure R- c ll \O wherein R and R are selected from the group consisting of hydrogen, halogen, cyanogen (CE N), hy-

droxyl, lactam and lactone groups and alkyl, aryl, alkaryl, aralkyl, and cycloalkyl groups such as methyl, ethyl, propyl, octyl, decyl, phenyl, tolyl, xylyl, benzyl, cyclohexyl and the like.

The preferred carboxylic monomers for use in this invention are the monoolefinic acrylic acids having the general structure wherein R is a member of the class consisting of alkyl groups having from 10 to 30 carbon atoms, preferably 12 to 22 carbon atoms and R is hydrogen or a methyl group. Representative higher alkyl acrylic esters are decyl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate and the corresponding methacrylates. Mixtures of two or three or more long chain acrylic esters may be successfully polymerized with one of the carboxylic monomers to provide useful thickening resins of this invention.

The preferred crosslinking monomer, if one is employed, is a polyalkenyl polyether having more than one alkenyl ether grouping per molecule. The most useful possess alkenyl groups in which an olefinic double bond is present attached to a terminal" methylene grouping, CI-I,=C They are made by the etherification of a polyhydric alcohol containing at least four carbon atoms and at least three hydroxyl groups. ,Compounds of this class may be produced by reacting an alkenyl halide, such as allyl chloride or allyl bromide with a strongly alkaline aqueous solution of one or more polyhydric alcohols. The product of such a reaction usually is a complex mixture of polyethers with varying numbers of ether groups on each molecule. Analysis of such materials, therefore, reveals only the average number of ether groupings on each molecule. Efficiency of the polyether cross-linking agent increases with the number of potentially polymerizable groups on the molecule. It is preferred to utilize polyethers containing an average of two or more alkenyl ether groupings per molecule.

In the monomeric mixture the two essential monomeric materials should be present in certain proprotions, although the exact proprotions will vary considerably depending on the characteristics desired in the polymer. Two-component monomeric mixtures of the carboxylic monomer and the long chain acrylic ester monomer preferably contain to 50 weight percent 5 carboxylic monomer and 5 to 50 weight percent acrylic ester monomer.

When the optional crosslinkin gflagent is present, polymeric mixtures containing about. 0.1% to about 4% by weight of crosslinking monomer based on the total of carboxylic acid monomer plus the long chain alkyl acrylate ester monomer, preferably 0.2% to 1.0% by weight based on the totalft'nixture are employed. Polymers containing less tha'rr5% to l% by weight of water extractable material are produced'with as little as 0.2% to 0.5% by weight of the crosslinker. When 0.1% to 4.0% more preferably 0.20 tO l .0% by weight of the crosslinking monomer is utilized,fwater-insoluble polymers are obtained, especially with acrylic acids, which are extremely water-sensitive, especially in the form of their monovalent salts, and swell greatly with the absorption of hundreds of times their own weight of water when neutralized with base. When 0.1 to 6.0%, more preferably 0.20 to 2.5% of the crosslinking monomer is copolymerized with maleic anhydride, high-swelling polymers also are obtained. In these interpolymers, the carboxylic monomer or monomers should not be less than 50% of the total monomeric mixture. Three component interpolymers may be made from monomeric mixtures comprising from 60% to 95% of a carboxylic monomer such as acrylic acid, from 39.9% to 4% by weight of a long chain acrylic ester such as lauryl acrylate and from 0.1% to 6% of crosslinking monomer such as polyallyl sucrose, the total parts by weight being equal to 100.

Preferred for use as crosslinked water-swellable artificial gums are tripolymers resulting from the polymerization of monomeric mixtures containing, respectively, from 70% to 95% by weight of acrylic acid, 4% to 29.5% of a second monomer such as lauryl acrylate or stearyl acrylate and 0.5% to 1.0% by weight of a crosslinker such as a polyallyl polyether. It is to be understood that in the above proprotions, if a maximum amount of two of the monomers are utilized that somewhat less than maximum amount of the third monomer must be utilized.

The polymers of this invention are preferably made by polymerization in an inert diluent having some solubilizing action on one or more of the monomeric ingredients but substantially none on the resultant polymer. Polymerization in mass may be employed but is not preferred because of the difficulty in working up the solid polymeric masses obtained. Polymerization in an aqueous medium containing a water-soluble free radical catalyst peroxygen is useful, the product being obtained either as a granular precipitate or as a highly swollen gel, either of which may be used directly or are easily further sub-divided and dried. Polymerization in an organic liquid which is solvent for the monomers but a non-solvent for the polymer, or in a mixture of such iblvents, in the presence of a solvent-soluble catalyst is most preferred because the product is usually obtained as a very fine friable and often fluffy precipitate which, after solvent removal, seldom requires grinding or other further treatment before use. Suitable solvents for the latter method include benzene, xylene, tetralin, hexane, heptane, carbon tetrachloride, methyl chloride, ethyl chloride, bromo trichloro methane, dimethyl carbonate, diethyl carbonate, ethylene dichloride, and mixtures of these and other solvents.

Polymerization in the diluent medium is carried out in the presence of a free radical catalyst in a closed vessel in an inert atmosphere and under autogenous pressure or artificially-induced pressure or in an open vessel under reflux at atmospheric pressure. Temperature of the polymerization maybe varied from 0C. to 100C, depending to a large degree on the molecular weight desired in the polymer. Polymerization under reflux at 50 to C. under atmospheric pressure using a free radical catalyst is generally effective in bringing a polymer yield of 75% to in less than 10 hours. Suitable catalysts include peroxygen compounds such as sodium, potassium and ammonium persulfates, caprylyl peroxide, benzoyl peroxide, hydrogen peroxide, pelargonyl peroxide, cumene hydroperoxides, tertiary butyl diperphthalate, tertiary butyl perbenzoate, sodium peracetate, sodium percarbonate, and the like as well as azo diisobutyryl nitrile, hereinafter referred to as azoisobutyronitrile. Other catalysts utilizable are the so-called redox" type of catalyst and the heavy-metal activated catalyst systems. These polymers generally do not attain their maximum properties in water until converted to a partial alkali, ammonium or amine salt. The neutralizing agent is preferably a monovalent alkali such as sodium, potassium lithium or ammonium hydroxide or the carbonates and bicarbonates thereof, or mixtures of the same, and also amine bases having not more than one primary or secondary amino group. Polyvalent bases such as calcium hyrdoxide usually have a deswelling action on the water-swollen polymers and their salts, although their absolute swell notwithstanding the presence of these polyvalent metal ions is higher than that of the naturally-occurring gum-like materials such as gum tragacanth and the like in the presence of the same deswelling agents.

Copolymers are evaluated as thickeners or viscosity improvers by mixing the copolymer with a base (typically triethylamine). The neutralized copolymer is dissolved in water. Solution viscosities are then measured with an RVT model Brookfield viscometer. The influence of salts, such as sodium chloride, upon the viscosities of these solutions is observed-by measuring viscosity upon the addition of incremental amounts of salt to the solutions.

The invention will now be more fully described in the following specific examples, which are intended as being illustrative only, of the preparation of several types of polymers using various proprtions of monomers, polymerization media, temperature, etc. and the effects of these polymers upon the viscosities of aqueous solutions.

EXAMPLE 1 A series of batch polymerizations of acrylic acid and stearyl acrylate was carried out in benzene at 65C. using caprylyl peroxide as the initiator. The reactions were conducted in 12 02. crown capped glass bottles under dry nitrogen. The polymers, insoluble in benzene, were separated by centrifuging and dried in a vacuum oven at 55C.

Weight percent stearyl acrylate content of the copolymers and appearance of solutions of 0.5 gram copolymer, 1 ml. of triethylamine and 100 ml. distilled water were as follows:

TABLE 1 Brookfield Viscosity cps Weight 74 Salt added grams Stearyl Appearance of Solution Polymer Acrylate no salt added None 0.05 0.1 0.2 0.3

A 8.3 smooth. clear. 100 B l 1.6 slightly, hazy. 1550 850 800 1750 2650 very stringy C 15.1 slightly hazy. 5750 3800 5750 9350 8800 very stringy D 21.9 hazy. very stringy. 7800 10450 12150 13500 12050 slightly grainy E 24.1 hazy. cloudy. very 7700 12800 13000 14500 10250 stringy. somewhat grainy F 25.8 cloudy, stringy. 7650 10900 11950 8950 5450 grainy Control* 42250 18500 9250 2950 1400 'Copolymcr of acrylic acid (98.5 weight percent) and nllyl sucrose 1.5 weight percent) swelling index 600.

The data show that copolymer solution viscosity increases through a maximum as the stearyl acrylate content of copolymer increases. Response of the solutions with respect to viscosity loss or increase as salt is added depends on the stearyl acrylate content of the copolymer used. The control water thickener of the prior art exhibits an initial greater viscosity in solution, but this viscosity falls drastically as increments of salt are added.

A control solution with only 0.2 parts salt present exhibits totally unsatisfactory viscosity of 2,950 cps while copolymers of the invention maintain viscosities up to change indicates that the salt can be used in conjunction with the polymers of the invention to not only control the solution viscosity as such, but also to control the consistency of the aqueous system.

EXAMPLE 2 Employing the procedure of Example 1, a series of acrylic acid-stearyl methacrylate copoly'mers was made and evaluated with results shown in Table 2.

TABLE 2 amount of salt is increased also rises to a maximum and then declines as weight percent stearyl methacrylate increases. Optimum weight percent stearyl methacrylate is determined by the concentration of the salt solutions that are to be thickened.

Again, the control solutions have fallen to unsatisfactory levels of viscosity (below about 3,000 cps.) when 0.2 part of salt is added. Similar solutions of the invention show viscosities up to 17,900 cps.

The neutralized acrylic acid-stearyl methacrylate copolymers form very viscous solutions even when present at low concentration by weight.

It is unexpected to find solutions of this type that increase in viscosity as sodium chloride is added.

Similar results were obtained when a series of copolymers and test solutions were made as in Example 1, except that lauryl acrylate was used as a replacement for stearyl acrylate.

EXAMPLE 3 Employing the procedure of Example 1, two series of acrylic acid-stearyl methacrylate polyallyl sucrose terpolymers was made and evaluated with results shown in Table 3. The test solutions comprised 1 gram of polymer, 2 ml. triethylamine and 100 ml. water. The first Brookficld viscosity cps Weight Salt added grams Stearyl Appearance of solution Polymer Methacrylatc no salt added None 0.05 0.1 0.2 0.3

A 4.4 clear. stringy 200 B 12.0 clear. very stringy 5600 3700 3350 7500 12300 C 18.5 clear. very stringy, 8500 7100 9400 17900 16050 slightly grainy- D 26.7 clear, stringy. 3150 6250 7450 l 1 8850 somewhat grainy E 33.4 clear. grainy, not 1400 2150 3700 4250 3500 so stringy. more buttery Control 42280 18500 9250 2450 1400 Copolymcr of acrylic acid (98.5 weight percent) and allyl sucrose 1.5 weight percent) swelling index 600 The data show that solution viscosity rises to a maximum, then falls off as the weight percent stearyl methacrylate increases. Resistance to viscosity drop as the series of terpolymer contained 0.5 weight percent crosslinker. The second series contained 1.0 weight percent crosslinker.

TABLE 3 Brookfield Viscosity cps Weight Weight Weight Percent Percent Percent Salt added grams Acrylic Stcaryl Polyallyl Polymer Acid Methacrylate Sucrose None 0.2 0.4 0.6 (1.8 2.0

TABLE 3-continued Brookficld Viscosity cps Weight Weight Weight Perccnt Perccnt Percent Salt uddcd grums Acrylic Steuryl Polyallyl Polymer Acid Mcthucrylutc Sucrose None 0.2 0.4 0.6 0.8 2.0

B 89.62 9.88 0.5 32900 30350 32900 36250 31500 6700 C 84.67 14.83 0.5 43650 41200 43000 38400 30600 1750 'D 79.75 19.75 0.5 52500 47450 40750 23800 15050 600 E 99.5 0.5 20500 9800 7300 5350 4250 1800 E is a prior art control thickcncr TABLE 4 F 93.95 5.05 1 0 61800 33850 27400 22650 14700 6650 C 91.25 9.75 1.0 61000 45450 39400 30250 21500 2850 H 84.38 14.62 1.0 56600 57400 42900 25750 18350 1050 J is a prior art control thickener EXAMPLE 4 Following the procedure of Example 1 a series of polymerizations was run wherein 95 mol percent of acrylic acid was copolymerized with 5 mol percent of a number of long chain alkyl acrylate esters wherein the chain length of the alkyl ester ranged from eight carbon atoms (exemplary of the prior art) to 18 carbon atoms. Solutions of one gram copolymer, 2 milliliters triethylamine and 100 ml distilled water exhibited viscosities as shown in Table 4.

Table 4 C Atoms in alkyl ester Viscosity A 18 octadecyl 45000 B 16 hexadecyl 26000 C 12 dodecyl 4500 D decyl 1000 E 8 octyl 350 F 6 hexyl 250 Increasing length of the alkyl ester chain leads to increasing viscosities. An unexpected sharp break point in viscosity increase occurs between chains of eight and 10 carbon atoms.

I claim:

1. An interpolymer of a monomeric mixture consisting essentially of from 95 to 50 percent by weight of an olefinically unsaturated carboxylic acid monomer and 5 to 50 percent by weight of an acrylic ester monomer of the formula wherein R is a member of the class consisting of alkyl groups having from 10 to 30 carbon atoms and R is selected from the group consisting of hydrogen and methyl.

2. An interpolymer of claim 1 wherein said carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and maleic acid.

3. A tripolymer of a monomeric mixture consisting essentially of from 60 to 95 percent by weight of an olefinically unsaturated carboxylic acid monomer, from 4 to 39.9 percent by weight of an acrylic ester monomer of the formula CH l-C-O-R wherein R is a member of the class consisting of alkyl groups having from 10 to 30 carbon atoms and R is selected from the group consisting of hydrogen and methyl, and 0.1 to 6.0 weight percent of a polymerizable crosslinking monomer containing a CH =C grouping and at least one other polymerizable grouping, the unsaturated bonds of said polymerizable grouping being non-conjugated with respect to each other.

4. The tripolymer of claim 3 wherein said cross-linking monomer is a polyalkenyl polyether of a polyhydric alcohol containing more than one alkenyl ether grouping per molecule, the parent polyhydric alcohol containing at least four carbon atoms and at least three bydroxyl groups.

5. A tripolymer of a monomeric mixture consisting essentially of from to percent by weight of acrylic acid, to 29.5 percent by weight of a member selected from the group consisting of lauryl acrylate, stearyl acrylate and stearyl methacrylate, and from about 0.5 to 1.0 percent by weight of the said monomers of a crosslinking monomer containing CH =C grouping and at least one other polymerizable grouping, the unsaturated bonds of said polymerizable grouping being nonconjugated with respect to each other.

6. The tripolymer of claim 5 wherein the said crosslinking monomer is a monomeric polyether of an oligosaccharide in which the hydroxyls which are modified are etherified with allyl groups, said polyether containing at least two allyl groups per oligosaccharide molecule.

7. A copolymer of a monomeric monoolefinic acrylic acid of the structure based on the total monomers of a monomeric acrylic R ester of the formula wherein R is a substituent selected from the class con- :lstmg of hydroienll crihlorme, bromme, hydroxyl, and groups having from to carbon atoms and R is see cyanogen group m( ?novdlem alkyl lected from the group consisting of hydrogen and aryl, aralkyl, alkaryl, and cycloaliphatlc hydrocarbon h L radicals, and from about 5.0% to about 50% by weight wherein R is a member of the class consisting of alkyl 

1. AN INTERPOLYMER OF A MONOMERIC MIXTURE CONSISTING ESSENTIALLY OF FROM 95 TO 50 PERCENT BY WEIGHT OF AN OLEFINICALLY UNSATURATED CARBOXYLIC ACID MONOMER AND 5 TO 50 PERCENT BY WEIGHT OF AN ACRYLIC ESTER MONOMER OF THE FORMULA
 2. An interpolymer of claim 1 wherein said carboxylic acid monomer is selected from the group consisting of acrylic acid, methacrylic acid, maleic anhydride and maleic acid.
 3. A tripolymer of a monomeric mixture consisting essentially of from 60 to 95 percent by weight of an olefinically unsaturated carboxylic acid monomer, from 4 to 39.9 percent by weight of an acrylic ester monomer of the formula
 4. The tripolymer of claim 3 wherein said cross-linking monomer is a polyalkenyl polyether of a polyhydric alcohol containing more than one alkenyl ether grouping per molecule, the parent polyhydric alcohol containing at least four carbon atoms and at least three hydroxyl groups.
 5. A tripolymer of a monomeric mixture consisting essentially of from 70 to 95 percent by weight of acrylic acid, 4 to 29.5 percent by weight of a member selected from the group consisting of lauryl acrylate, stearyl acrylate and stearyl methacrylate, and from about 0.5 to 1.0 percent by weight of the said monomers of a crosslinking monomer containing CH2 C< grouping and at least one other polymerizable grouping, the unsaturated bonds of said polymerizable grouping being nonconjugated with respect to each other.
 6. The tripolymer of claim 5 wherein the said crosslinking monomer is a monomeric polyether of an oligosaccharide in which the hydroxyls which are modified are etherified with allyl groups, said polyether containing at least two allyl groups per oligosaccharide molecule.
 7. A copolymer of a monomeric monoolefinic acrylic acid of the structure 